SQ10403

INTRODUCTION TO AQUATIC CHEMISTRY AND POLLUTION

Importance of aquatic chemistry Water: basic molecules, bonding & structure Unique properties of water Hydrological cycles Seawater and Freshwater, isotopes of hydrogen and oxygen Characteristics of water: physical, chemical and biological

Advantages of the chemical perspectives include:

Huge potential information due to high number of elements (93), isotopes (260), naturally occurring radioisotopes (78) and compounds (innumerable) present in aquatic system, mainly in ocean Chemical measurement have high re-presentativeness, reproducibility and predictability (Statistically meaningful) Quantitative treatment are possible (Balances, prediction of reaction rate and extents, age estimates). All the normal rules of chemistry apply. Chemical changes indicate processes and integrated the net effect of multiple previous events. Most of the ocean is inaccessible to direct observation and past environmental records are preserved in ecosystem.

Aquatic chemistry is the Most Interdisciplinary

Chemical components of water influences the water quality and thus effect its aquatic life Biological process in the aquatic ecosystem are controlled by the chemistry. Biological process are an important control on chemical distributions. Biology, chemistry & geology form new sub-discipline called biogeochemistry What control chemical distribution helps us to understand nutrients dynamics Anthropogenic chemical deposition makes the system complex, specially aquatic pollution

Structure of water
Water is composed of H2O molecules and their dissociation products OH- (the hydroxyl ion) and H+ (the hydrogen ion; or more appropriately represented as H3O+, the hydronium ion). A molecule of water consists of one large atom of oxygen and two smaller atom of hydrogen, bonded together co-valently, arrangement is in V shape with an angle of 105O.

Under certain conditions, an atom of hydrogen is attracted by rather strong forces to two atoms instead of only one, so that it may be considered to be acting as a bond between them. Hydrogen bonds among This is called hydrogen bond.
The small electronegative atoms O and N are somewhat negatively charged when they are bonded to hydrogen atoms. The negative charges on O and N attract the slightly positive hydrogen atoms, forming a strong interaction called hydrogen bond
H \ O / H water molecules

/
....

H-O \ H

H /
. . . .O

. . . .O

\ H H-O . . . H | | H . . . O--H

As water heats, more hydrogen bonds break, and converting water to a liquid state, mixture of individual and aggregated molecules.

Oxygen is an "electronegative" or electron "loving" atom compared with hydrogen. Water is a "polar" molecule, meaning that there is an uneven distribution of electron density. Water has a partial negative charge (-) near the oxygen atom due the unshared pairs of electrons, and partial positive charges (+) near the hydrogen atoms.
An electrostatic attraction between the partial positive charge near the hydrogen atoms and the partial negative charge near the oxygen results in the formation of a hydrogen bond as shown in the illustration.

The ability of ions and other molecules to dissolve in water is due to polarity. For example, in the illustration here sodium chloride is shown in its crystalline form and dissolved in water.

Although some chemical compounds that dissolved in water remain in their molecular form (e.g., O2, N2, CH3CH2OH etc.), many dissociate into positively and negatively charged ions (e.g. NaCl Na+ + Cl-). In chemical terminology: - a cation is a positively charged ion - an anion is a negatively charged ion

In both freshwater and seawater, the major cations usually are Ca2+, Mg2+, Na+ and K+, whereas the major anions usually are HCO3-, Cl- ad SO42-, but in different proportion as shown in pie-chart

Limnologist and aquatic toxicologist are steeped in the tradition of expressing concentrations of molecules or ions as mass per unit volume (e.g. mg/liter), It is more convenient for equilibrium-thermodynamic calculations when concentrations of dissolved substances are expressed as moles per unit volume (e.g. moles/liter or M as morality).
As for example, to prepare 1M of NaOH solution, dissolved 40grams of NaOH (molecular weight of NaOH = 40) into 1 liter of distilled water.

Geochemists tend to express concentrations as moles/kg, because these units are useful when working with high concentration mixtures such as salt brines.

In general, the following abbreviations for mass concentration units are often encountered:
ppt= parts per thousand = grams per liter=g/liter ppm= parts per million=milligram per liter=mg/L=10-3/liter ppb= parts per billion=micrograms per liter= g/L=10-6/liter ppt = parts per trillion=nanograms per liter =ng/L=10-9/liter

It is important to note that pptis used to designate two totally different mass concentration units: to oceanographers and limnologists, ppt is parts per thousand (g/liter); whereas to toxicologist ppt usually designates parts per trillion (10-9/liter).

So, to avoid confusion do not use ppt, ppm and ppb.

Due to nature of the physical arrangement of its hydrogen atoms and its hydrogen bonds, water is unique substance.

Water is unique: Water has numbers of unique properties and some of them are related to hydrogen bonding 1. Water is the most abundant in earth covering more than 70% of the globe 2. Ocean is about 2.5 times more extensive than land, they are habitable throughout their depth, and the sea provides more than 300 times of living space. 3. Water has a high specific heat: water can store high quantities of heat energy with a small rise in temperature

4. High latent heat of fusion and latent heat of evaporation. These facts play a very important role in the heat regulation of organisms themselves. 5. Water has relatively high freezing point. As large amount of heat, this must be given up before water can turn into ice. So, ocean and lakes freeze only at the surface. Even ponds rarely freeze to the bottom. 6. Water is a good solvent. The extent of ionization of solutes in water is extremely high, providing the possibility of a great variety of radicals and of chemical recombination.

7. Water has the highest surface tension of any common substances except mercury. 8. Water provide transporting medium 9. The essential purposes of the proper concentration of water must be maintained in side the organism. During starvation, for example man may loss as much as 40% of body weight including half of the protein and nearly all the glycogen and fat without serious danger, but if 10% of the water content of the human body is lost, serious disorders resulted

Hydrological cycle of water

The water cycle is also known as the hydrological cycle.

Basically, water moves from the Earth to the atmosphere, and from the atmosphere back to the Earth in a never ending cycle.

Evaporation: The sun heats the Earth's suface water turning the water into vapor. This is known as evaporation Transpiration is the process where plants give off water vapor. Water vapor that animals sweat and breathe out (including humans) also evaporates and goes into the atmosphere. Precipitation can take the form of rain, snow, or sleet

Factors controlling the composition of natural water are extremely varied. These include physical, chemical nature and changes with the biological process. The physico-chemical properties of water are controlled by the hydrological cycle The gaseous sulfur dioxide component of the sulfur cycle and the nitrogen oxide of the nitrogen cycle mix in the atmosphere. These are the major pollutant elements in the atmosphere. Some of this mixture returns to Earth as particulate matter and airborne gases, known as dry deposition. A major portion is transported away from the source by wind driven process.

During their atmospheric transport SO2 and NO2 and their oxidative products participate in complex reactions involving hydrogen chloride and other components, oxygen and water vapor. These reactions dilute solutions of strong acids, notably nitric acid and sulfuric acid. Eventually they come to Earth in acidic rain, snow, and fog known as wet deposition.

Not only sulfur and nitrogenous compounds, the precipitation falls on lands and surface runoff carries various substances and more highly mineralized. Water flow across vegetation areas also dissolved various organic compounds and particulate organic matters both organic and inorganic.

Flora and fauna inhabited in aquatic ecosystem goes through various biological processes that also controlled the nature of water. The nutrient generations by various microbes in soil and water influences the availability of composition of nutrients in natural water. The nutrient flow through food chain and control the complex biological process

Physical characteristics of water

Temperature: Basically important for its effects on other properties e.g. speed up chemical reaction, reduction the solubility of gases amplification of texture and order. Water temperature mainly controlled by the air temperature and fluctuated with the various seasons. Thermal stratification is the result of seasonal variations in natural lakes and ponds contributes in nutrient remixing and changes the properties of water.

Taste and odor: Due to dissolved impurities, which are often organic in nature, such as hydrocarbon those containing phenol and benzene the taste and odor changes.

Color: Pure water is colorless, natural water color is due to suspended matter. Yellow color natural water indicates the availability of humus substances, which is not harmful or may be due to the presence of acid sulfate soil, which is harmful.

Turbidity: The presence of solids gives the liquid cloudy appear, unattractive and may be harmful. Turbidity due the presence of phytoplankton of course contributed in food chain, but if due to clay may causes severe problem in ecosystem. Conductivity: Measure of its ability to convey an electrical current. The greater the concentration of ions in natural water, the larger the conductivity. Distilled water has a conductivity of about 1mhos/cm, while in freshwaters normally have conductivities of 20 to 1500mhos/cm. In principal in brackish water the conductivity may be used to obtain reliable estimates of salinity or total dissolved solids.

Chemical characteristics of water pH: The pH is defined as the negative logarithm of the hydrogen ion activity as by formula: pH = -log(H+) The pH scale usually is shown to extend from 0 to 14. The intensity of acidity and alkalinity of water is measure with this range of scale. Although pH 7 generally taken as the neutral point of water, this convention is strictly correct only at 25oC, where Kw (Ionization constant) = 10-14. For example, at 35oC the neutral point is; [H+] = 2.1 x 10-14 = 10-13.68 (ionization constant at 35oC is 2.089) [H+] = 10-6.84 pH = 6.84

Oxidation-reduction potential: A substance is oxidized if it loses electrons and reduced if it gains electron. Every oxidation requires a corresponding reduction to balance electron. The substances gaining electron is an oxidizing agent and the substance losses electro is reducing agent. Oxidation-reduction may be illustrated as: Fe3+ + e- = Fe2+ If an electron is removed from Fe2+ (Ferrous iron) it is oxidized to Fe3+ (Ferric iron). Ferric iron is reduced to ferrous iron when it gains an electron.
The oxidation-reduction or redox potential of a solution is a measure of the proportion of oxidized to reduced substances. The redox potential is measured with respect to a hydrogen electrode and is called Eh, the unit is volt.

Alkalinity: Alkalinity is due to the presence of HCO3-, CO32- or OH-. Most of the alkalinity in natural is due to the HCO3- and produced by the action of ground water on limestone. According to ionic composition alkalinity may be divided into bicarbonate alkalinity, carbonate alkalinity and hydroxide alkalinity. CaCO3 + H2O + CO2 Ca(HCO3)2 Alkalinity is useful as it provides buffering to resist changes in pH. The terms hard and soft water often used by limnologists in alluding to waters of high and low alkalinity.

Hardness: Hardness was formerly used to describe the ability of water to precipitate soap. Limnologist express hardness as the sum of the separate ionic concentrations of calcium and magnesium. So, hardness is mainly due to the presence of Ca2+ and Mg2+. The calcium hardness is simply the calcium concentration expressed as equivalent calcium carbonate. If total alkalinity and total hardness are equal, calcium and magnesium can be thought of as being associated entirely with bicarbonate and carbonate.

Following topics will be discussed later Dissolved oxygen Carbon dioxide Biological oxygen demand Chemical oxygen demand Nitrogen Phosphorus Sulfur Biological characteristics: Photosynthesis and Chemosynthesis Phototrophs, Heterotrophs, Saprotrphs, Phagotrophs